There is an ongoing need to generate new phosphor compositions to improve efficiency and color quality in luminescent devices, particularly in the production of white light. Phosphors are luminescent materials that can absorb an excitation energy (usually radiation energy) and store this energy for a period of time. The stored energy is then emitted as radiation of a different energy than the initial excitation energy. For example, “down-conversion” refers to a situation where the emitted radiation has less quantum energy than the initial excitation radiation. Thus, the energy wavelength effectively increases, and this increase is termed a “Stokes shift”. “Up-conversion” refers to a situation where the emitted radiation has greater quantum energy than the excitation radiation (“Anti-Stokes shift”).
Improvements in efficiency and color quality in phosphor-based devices are constantly being developed. “Efficiency” relates to the fraction of photons emitted with respect to a number of photons initially provided as excitation energy. Inefficient conversion results when at least a portion of the energy is consumed by non-radiative processes. Color “quality” can be measured by a number of different rating systems. “Chromaticity” defines color by hue and saturation. “CIE” is a chromaticity coordinate system developed by Commission Internationale de l'Eclairage (International commission on illumination). The CIE Chromaticity Coordinates are coordinates that define a color in “1931 CIE” color space. These coordinates are defined as x, y, z and are ratios of the three standard primary colors, X, Y, Z (tristimulus values), in relation to the sum of the three tristimulus values. A CIE chart contains a plot of the x, y and z ratios of the tristimulus values versus their sum. In the situation where the reduced coordinates x, y, z add to 1, typically, a two-dimensional CIE (x, y) plot is used.
White-like colors can be described by a “correlated color temperature” (CCT). For example, when a metal is heated, a resulting light is emitted which initially glows as a red color. As the metal is heated to increasingly higher temperatures, the emitted light shifts to higher quantum energies, beginning with reddish light and shifting to white light and ultimately to a bluish-white light. A system was developed to determine these color changes on a standard object known as a blackbody radiator. Depending on the temperature, the blackbody radiator will emit white-like radiation. The color of this white-like radiation can then be described in the CIE chromaticity chart. Thus, the correlated color temperature of a light source to be evaluated is the temperature at which the blackbody radiator produces the chromaticity most similar to that of the light source. Color temperature and CCT are expressed in degrees Kelvin.
A “color rendering index” (CRI) is established by a visual experiment. The correlated color temperature of a light source to be evaluated is determined. Then eight standard color samples are illuminated first by the light source and then by a light from a blackbody having the same color temperature. If a standard color sample does not change color, then the light source has a theoretically perfect special CRI value of 100. A general color rendering index is termed “Ra”, which is an average of the CRIs of all eight standard color samples.
Older white lamps involved emission of light over a broad wavelength range. It was then discovered that a white-like color can be simulated by a mixture of two or three different light colors, where each emission comprised a relatively narrow wavelength range. These lamps afforded more control to manipulate the white color because emissive properties (emission energy and intensity) of the individual red, green and blue light sources can be individually tailored. This method thus provided the possibility of achieving improved color rendering properties.
An example of a two-color lamp comprises one phosphor and an excitation energy source. Light emitted by the phosphor combines with unabsorbed light from the excitation source to produce a white-like color. Further improvements in fluorescent lamps involved three different light colors (i.e. a tri-color lamp) resulting in white light at higher efficiencies. One example of a tri-color lamp involved blue, red and green light-emitting phosphors. Other previous tri-color lamps comprised a combination of light from two phosphors (a green and red phosphor) and unabsorbed light from a mercury plasma excitation source.
Previous tri-color lamps involving a mercury plasma excitation source, however, suffer many disadvantages including: (1) a need for high voltages which can result in gaseous discharge with energetic ions; (2) emission of high energy UV quanta; and (3) correspondingly low lifetimes. Thus, there is an ongoing need for devices that overcome these deficiencies.
WO 01/24229 discloses to a tri-color lamp for generating white light. In particular, WO 01/24229 relates to a phosphor mixture comprising two phosphors having host sulfide materials that can absorb radiation emitted by a light emitting diode, particularly a blue LED. This arrangement provides a mixing of three light sources—light emitted from the two rare earth ion, to allow matching of the phosphors in relation to the LED emitted radiation. Power fractions of each of the light sources can be varied to achieve good color rendering. WO 01/24229 also relates to an alternative to a green LED comprising a single green phosphor that absorbs radiation from a blue LED. A resulting device provides green light of high absorption efficiency and high luminous equivalent values.
There remains a continued challenge to uncover phosphor compositions and mixtures of these compositions to provide improved properties, including improved efficiency, color rendering (e.g. as measured by high color rendering indices) and luminance (intensity), particularly in a tri-color, white lamp.
It has been observed that photoluminescent phosphor compounds have characteristic ranges of luminescent quenching temperatures. That is, when the phosphor is excited into luminescence as for example by subjecting the same to radiation from a source of ultraviolet light, the intensity of the luminescence will gradually decrease as the temperature of the phosphor is raised through a specified range of temperatures. For example, the compound Zn.80 Cd.20 S:AgCl will gradually quench from bright green, to dull green, to green gray, to gray, to black, as the temperature is increased from 95° C. to 105° C. The temperature ranges of the compounds provided by the afore described basic phosphor system are found to be determined by the composition of their anionic component. Phosphor compounds may be therefore made to have different quenching temperature ranges as well as different color characteristics. The thermal quenching at higher temperatures reduces the LED efficiency, in particular at high chip temperatures. Therefore it is desirable to replace sulfide phosphors by non-sulfide phosphors with a higher thermal quenching temperature.